Process for producing rot and wrinkle resistant cellulose containing textile and textile obtained therewith



United States Patent 3,311,496 PROCESS FOR PRODUCING ROT AND WRINKLE RESISTANT CELLULOSE CONTAINING TEX- TILE AND TEXTILE OBTAINED THEREWITH William Julius van Loo, Jr., Middlesex, N.J., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed Feb. 18, 1964, Ser. No. 345,608 7 Claims. (Cl. 117-1385) The present invention relates to processes for improving the wrinkle resistant properties of textile materials and to the textile materials so finished. More particularly, the invention relates to processes for improving the wrinkle resistance or crease resistance properties of a textile material without a corresponding loss in tensile strength.

Heretofore, cellulose containing textile materials have been treated with creaseproofing resins to impart wrinkle recovery properties to the materials. These creaseproofing resins were generally applied to fabrics free from sizes or other finishes and, while they improved the wrinkle recovery properties of the fabrics, there was always suffered a loss in tensile strength. Thus, in general, the higher the wrinkle resistance, the lower the tensile strength of the materials treated.

Suitable creaseproofing .resins are those of the hardenable aminoplast type which are applied to the materials in a water-soluble state and then dried and cured. However, while the fabric which has been finished with these condensates is characterized by improved wrinkle resistance, the effect of the curing of the resin whereby crosslinking of the cellulose molecules is affected, results in reducing the tensile strength of the material. Therefore, a process is needed which will not only improve the wrinkle resistance but will achieve such improvement with little or no loss in tensile strength.

Accordingly, it is an object of this invention to provide a process which can achieve this result.

It is also known that cellulosic textile materials can be treated with hardenable aminoplasts to render the materials resistant to the attack of micro-organisms. However, while a degree of rot resistance was obtained from these resins, it was accompanied by a loss in the tensile strength of the materials.

In US. Patent No. 2,763,574 there is described a wet steam process for treating materials with these hardenable aminoplasts, whereby rot resistance is imparted to the textiles without a loss of tensile strength. This wet steam process will be more fully described hereinafter. While the type of finishing described in the above-identified patent imparts rot resistance to the textiles, it does not impart any other improvements in the major physical properties often desired in fabrics, such as wrinkle recovery.

Applicant has found that, by applying the rot resistant resin by the Wet steam process along with a crease resistant resin, new and unexpected results are obtained. Not only are the advantageous properties of each resin retained, but in addition a synergistic effect with respect to the wrinkle recovery properties is obtained, which in turn leads to an improved wrinkle recovery-tensile strength relationship.

The subsequent examples will show that if a cellulosic textile material is treated with a hardenable aminoplast by the wet steam process as described in US. Patent No. 2,763,574, it has rot resistance with no loss in tensile strength, but there is also no wrinkle recovery. Whereas, if it is treated merely with a crease resistant hardenable aminoplast resin and dried and cured conventionally, it

. for the release of potential pressure build-up, but insufliciently large to allow for the significant escape of mois- 3,311,496 Patented Mar. 28, 1967 has Wrinkle recovery, but With a loss of tensile strength.

Applicants invention involves pretreating the textile materials with hardenable aminoplasts by the wet steam process before treating with a creaseproofing hardenable aminoplast. Applicant has found that by this process not only are wrinkle recovery properties retained, but the value of the wrinkle recovery of the material is greater when it has been pretreated by the Wet steam process which by itself imparts no wrinkle recovery. In addition, at a given level of Wrinkle recovery, after being treated with the creaseproofing resin, the tensile strength of the wet steam pretreated fabric is significantly higher than that of an unpretreated fabric which gives rise to the greater wrinkle recovery-tensile strength relation. The material also retains the rot resistance imparted by the wet steam process so that fabrics so finished have both rot resistance and a high order of wrinkle recovery.

The Wet steam process as described in the above-identified patent is essentially a process wherein the hardenable aminoplast is cured on the fabric in the presence of about 45% of the Water in the original impregnating aqueous resin solution. By fixing the aminoplast with little or no drying of the impregnated fibrous material, the tensile strength properties are retained. The aminoplast and curing catalyst therefor are applied to the fabric during the wet steam process by any conventional method from an aqueous solution. The fabric is then rolled up tightly on a dowel, rod or shell and placed in a suitable essentially closed container. As noted, the container is essentially closed, but is fitted with a small opening to allow ence of moisture without substantial drying and these are all within the scope of applicants invention.

Suitable hardenable aminoplasts which can be used to pretreat the fabric by the wet steam process include condensation products of formaldehyde or its equivalent with compounds such as urea, thiourea, cyanamide, dicyandiamide, biguanide, melamine, formoguanamine, acetoguanamine and the like, including their alkyl and acyl derivatives. Particularly suitable are the water-soluble condensation products of melamine and formaldehyde, and in particular the methylol or methoxymethyl derivatives of melamine. This includes methylated melamine-formaldehyde condensates, including hexa(methoxymethyl)- melamine, and as a preferred condensate dimethylol melamine is cited. Advantageously, a curing catalyst is added to the solutions of the aminoplast. Suitable catalysts include diacetin, monochlorohydrin, dichlorohydrin, glycol as previously described through general methods of application such as spraying, dipping, immersion or padding.

Generally, they are applied in amounts of from 1.0 to 30.0% of resin solids based on the dry weight of the fabric with the preferred range being from 5.0 to 15.0%. The resin solutions generally include a curing catalyst amounting to 2.5 to 25.0% based on the weight of the resin with the preferred range being from 5.0 to 15.0%. When properly processed, the treated textile material will show approximately or higher of the initial amount of resin durably afiixed, the amount of resin fixation being determined by nitrogen analysis.

The cellulosic textile materials which can be used include cotton, rayon, linen, hemp, jute or the like. They may be present in combination with up to 50% of other natural or synthetic fibers such as wool, acetate, nylon, polyester fibers, acrylic fibers, as for example those sold commercially as Creslan, Orlon, Acrilan and the like. Preferably, the textile material is a formed woven cotton fabric.

Creaseproofing resins used in the second step of the two-step process refer to those resins employed by the textile finishing industry to impart wrinkle recovery to cellulosic textile material. These materials are usually compounds having more than one functional group available which is capable of reacting with the cellulose fiber to form cross-links therewith, whereby wrinkle recovery is imparted to the material. These agents, hereinafter referred to as after-treatment resins, may be any type of aminoplast. Particularly, the after-treatment resins include urea-formaldehyde condensates, including the cyclic urea-formaldehyde condensates, such as dimethylol ethylene urea, dimethylol 1,2-propylene urea, dimethylol 1,3- propylene urea, uron formaldehyde condensates, triazone formaldehyde condensates, tri-azine-formaldehyde condensates such as melamine-formaldehyde, guanamineformaldehyde condensates, as well as the alkylated and in particular the methylated derivatives of these and other aminoplast resins. Curing catalysts are often used with these hardenable aminoplast crease resistant materials, and they may be metal salts such as the chlorides and nitrates of magnesium, zinc and aluminum. Amine and alkanolamine salts such as ethanol amine hydrochloride may also be employed as catalysts. The preferred aftertreatment resin for imparting the crease resistant properties is dimethylol ethylene urea with a magnesium chloride catalyst.

These after-treatment agents are applied in the form of an aqueous solution in an amount of from 1.0 to 15.0% of resin solids based on the weight of the fabric. The curing catalyst is usually about 2.5 to 25.0% based on the weight of the resin. The after-treatment resin is usually dried at about 150 to 400 F. for anywhere from .25 to 3.0 minutes. It is then cured at about 250 F. to 500 F. for anywhere from .5 to 3.0 minutes. Since, in general, time and temperature are inversely proportional, i.e., as the time increases, the temperature may be lowered and as the time decreases, the temperature may be elevated, wide limits of time and temperature can be employed.

The after-treatment resin may be applied by any conventiorral means such as spraying, dipping, immersion or padding. The preferred method is by padding as through a microset padder.

Thus, by combining a wet steam process for applying a rot resistant or pretreatment resin to a textile with the conventional process for applying a creaseproofing or after-treatment resin to the same textile, new and unexpected results are obtained. The results in the following examples show that a greater wrinkle recovery is generally obtained on the pretreated fabric than on the unpretreated fabric when equal concentrations of the aftertreatment resin are used at all levels of the wet steam process. In addition, the tensile strength-wrinkle recovery relationship is greater for the wet steam pretreated fabric than for the unpretreated fabric after the application of the crease resistant resins. There is also obtained a combined finish for textiles which imparts thereto both rot resistance and wrinkle recovery.

In order that the present invention will be more fully understood, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated.

4 Example 1 Cotton percale x 80) was treated with the following aqueous solutions by padding through a rnicroset padder to impart wrinkle recovery properties to the fabric. The aqueous solutions are designated A, B and C.

The dimethylol ethylene urea was diluted with part of the water and the magnesium chloride was added thereto. The solutions were then brought to total weight with the remaining water.

The fabric samples, which had obtained a wet pick-up of were dried for 2 minutes at 225 F. and cured for 1.5 minutes at 350 F. in a circulating hot air oven.

The wrinkle recovery of each fabric was measured on a Monsanto wrinkle recovery tester, the values reported in degrees, following the tentative test method of 66-1956 described on page 158 of the 1957 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, vol. 33.

The tensile strength was measured on a Scott Tester according to ASTM standards.

In Table II are shown the results of the tests run on the fabrics treated as described above. The headings A, B and C correspond to the same headings in Table I.

Percent resin solids applied.

Table II shows that by treating the cotton textile materials in the manner described, there is an increase in the wrinkle recovery properties of the materials, but there is also a corresponding loss in fabric strength.

Example 2 Cotton percale (80 x 80), the same as used in Example 1, was treated with a bath containing 15% solids of dimethylol melamine and 10% diacetin based on the weight of the resin, as a catalyst, by the wet steam process as previously described. The wet fixation time was 2.5 hours.

To show the "amount of resin durably bound to the fabric, a sample of the fabric was boiled in water for /2 hour, and the resin fixation was measured by analysis for nitrogen to be 10.8% based on the weight of the fabric. This is 97.6% of the finish initially present.

These cotton materials were then treated with the solutions A, B and C described in Example 1.

Wrinkle recovery and tensile strength tests were then run on the fabrics by the methods described in Example 1. For control purposes, one sample was treated only with the dimethylol melamine and diacetin and this is desig nated as pretreated only in Table III.

The headings A, B and C correspond. to the same headings in Table I.

5 6 TABLE III The results show that there is a marked increase in the wrinkle recovery properties of the dimethylol ethylene p t t d A B C urea treated fab ric when it has been pretreated with diy 17* 2 57 57 methylol melamine by the wet steam process over the unpretreated ones. Mere pretreating alone does not affect g the wrinkle recovery properties, but when used in com- 142 253 264 278 bination with the crease resistant resins a synergistic effect Tensile Strength (Warp-i-Filli obtai d Pounds) 107 82 73 66 The results indicate that this synergistic effect and a 10 greater tensile strength-wrinkle recovery relationship are Percentresm Sohds applied obtained at all levels of the wet steam process. Therefore, the results are not recessively dependent upon fixa- By compangg the results of g H and Table tion during the wet steam process. However, the data a :5 f i i g e cotton matena S indicates that better results are obtained when the dig 1met me Y b Wet steam lf 15 methylol melamine fixation is high as a result of the wet as It If ect on e 6 recovery or l steam process than where the fixation is low. strength properties of the material over that which 16 untreated. However, it clearly illustrates that if the Example 4 materials are pretreated by the wet steam process, before they are treated with the crease resistant solutions, 20 Spun rayon h lli as treated with 15% solids of dithat a synerglsflc efiect Wlth E P? t0 t Wrlnkl methylol melamine by the wet steam process as previously covery propertles of the materials 1s obtalned. By 00 described. The wet fixation time was 2.5 hours and the p n n 0f l wn A p n Increase of 57 resin fixation value obtained was 98% of that initially grees or nearly 30% was realized when the materials t, W pretljeatei It call 3150176 Seen that a g i Value The pretreated fabrics were then treated by padding 1n the wrinkle recovery-tensile strength relationship can through a mi r et padder with the following aqueous be obtained. At a given level of wrinkle recovery, for l ti example, around 250 degrees, the tensile strength of the After obtaining a wet pick-up of 100%, they were pretreated fahl'lc 1'5 32 P which is n ly g r dried and cured by the method as set forth in Example 1. than that of the unpretreated fabric which is 63 pounds.

TABLE VI Example 3 Parts by Weight Cotton percale (80 x 80) was treated with 2.5, 5.0, 7.5, 10 and 15 solids of dimethylol melamine by the wet 35 G H steam process as previously described.

These fabrics were then treated with the aqueous solu- I L8 2 tions described in Table IV by microset padding. Total, with water 400 400 After obtaining a wet pick-up of 85%, they were dried and cured by the method as set forth In Example The fabrics were then tested for their wrinkle recovery and tensile strength and the results of these tests are TABLE IV shown in Table VII.

Parts by Weight TABLE VII D E F Untreated Dimcthylol Ethylene Urea Fabric Dimethylol ethylene urea 11.8 29.4 58.8 et e tment Re Zinc nitrate 1. 41 3. 54 7.08 G E Total, with water 1,000.0 1,000.0 1, 000.0

W.R. T.S. W.R. T.S.

The fabrics were then tested for their wrinkle recovery Unpmtreated 212 110 246 91 269 and tensile strength and the results of these tests are shown 185 117 265 275 87 in Table V.

TABLE V Untreated Fabric Dimethylol Ethylene Urea Percent Solids of Pretreatment Resin (Percent Resin Fixation) D E F W.R.1 'l.s.

W.R 'r.s. W.R T.S. W.R T.S.

Unpretreatecl 150 112 180 223 77 248 64 2.5% dimetllylol melamine (51%) 161 113 205 98 223 87 264 74 5.0% dimethylol melamine s4%) 162 210 96 247 1 so 267 71 7.5% dimethylol melamine (5l%) 159 109 219 89 249 77 270 68 10.0% dimethylol melamine (71%) 163 111 223 89 257 72 27s 65 15.0% dimethylol melamine (92% 164 111 235 83 271 70 289 62 15.0% dirnethylol melamine 3 7%) 165 112 235 64 200 61 265 59 15.0% dimethylol melamine 4 (2%)- 108 238 71 266 60 268 61 15.0% dimethylol melamine 5 (2%) 158 112 243 58 256 5a 264 57 1 Wrinkle Recovery, W-l-F in degrees.

2 Tensile Strength, W-l-F in pounds.

3 Wet Steam Process, Cured 1.5 hrs. at 210 F: 4 Wet Steam Process, Cured 1.0 hr at 210 F 5 Wet Steam Process, Cured .5 hr. at 210 F.

The data clearly shows a greater degree of wrinkle recovery is obtained on fabrics other than cotton when it is also wet steam pretreated than on unpretreated fabric at equal concentrations of dimethylol ethylene urea. At a given level of wrinkle recovery, tensile strength of the wet steam pretreated fabric is significantly higher than that of the unpretreated.

Example Cotton percale (80 x 80) was treated with dimethylol melamine by the wet steam process as previously described. The wet fixation time was 2.5 hours and the resin fixation value obtained was 54% The pretreated materials were then treated by padding through a microset padder with an aqueous solution containing 14.7 parts by weight dimethyl ether or trimethylol melamine, 14.2 parts by Weight of magnesium chloride in a total of 200 parts by weight with water as the diluent.

The fabrics obtained a wet pick-up of 85% and were dried and cured by the method as set forth in Example 1.

The fabrics were then tested for their wrinkle recovery and tensile strength and the results of these tests are shown in Table VIII.

TABLE VIII Dirnethyl Ether oi Untreated Trimethylol Pretreatment Resin Melamine W.R. T.S. W.R. T.S.

Unpretreated 168 98 248 58 Dirnethylol melamine 156 102 270 58 Example 6 Cotton percale (80 x 80) was treated with (1) 10% solids of a methylated melamine formaldehyde condensate and (2) 10% solids of a hexa(methoxyrnethyl)melamine resin by the wet steam process as previously described. The wet fixation time in both instances was 2.5 hours.

The pretreated materials were then treated by padding through a microset padder with an aqueous solution of 5% solids dimethylol ethylene urea resin plus 12% solids magnesium chloride and the remainder water. The fabrics were then dried and cured by the method as set forth in Example 1.

The fabrics were then tested for their Wrinkle recovery and tensile strength and the results of these tests are shown in Table IX.

The data clearly shows that other pretreatment resins besides dimethylol melamine also result in a synergistic 8. effect on the wrinkle recovery properties obtained on the wet steam pretreated fabric than that which is obtained on unpretreated fabrics at equal concentrations of dimethylol ethylene urea. Also, a better tensile strength-wrinkle recovery relationship is obtained.

It will be appreciated that any stage in the above-described process other textile finishing agents and auxiliaries may be employed, such as softeners, lubricants, brighteners, buffers, odors, and the like.

I claim:

1. A process for imparting to cellulose-containing textile materials improved wrinkle recovery with low tensile strength losses, which comprises treating the material with an aqueous impregnating solution of an aminoplast containing a curing catalyst so as to apply from 1% to about 30% based on the weight of the material of said aminoplast, curing said aminoplast impregnated material in the presence of water without substantially drying the material, subsequently applying to said treated material an aqueous solution of a water-soluble creaseproofing hardenable aminoplast containing a curing catalyst so as to apply from 1% to about 15 based on the dry weight of the material of said aminoplast and heat curing the thus treated material.

2. A process according to claim 1 wherein the creaseproofing hardenable arninoplast is a melamine formaldehyde condensate.

3. A process for imparting to cellulose-containing textile material improved wrinkle recovery with low tensile strength loss, wihich comprises treating the material with an aqueous impregnating solution of a melamine formaldehyde condensate and a curing catalyst therefore so as to apply from 1.0% to about 30% based on the dry weight of the textile material of said condensate, curing said condensate impregnated material in the presence of water, without substantially drying the material, subsequently applying to said treated material an aqueous solution of a water-soluble creaseproofing hardenable aminoplast containing a curing catalyst therefor so as to apply from 1% to about 15% based on the dry Weight of the material of said aminoplast, and heat curing the thus treated material.

4. A process according to claim 3 wherein the melamine formaldehyde condensate is dimethylol melamine and the hardenable aminoplast resin is dimethylol ethylene urea.

5. A cellulose-containing textile material having an improved wrinkle recovery with low-tensile strength loss, having thereon from 1% to about 30% based on the dry weight of the material of a wet cured melamine formaldehyde condensate and from 1% to about 15% base-d on the dry weight of the material of a dry cured creaseproofing hardenable aminoplast.

6. A textile material as defined in claim 5 wherein the crease resistant hardenable aminoplast resin is a member of the group consisting of melamine formaldehyde and urea formaldehyde condensate.

7. A cellulose-containing textile material having an improved wrinkle recovery with low tensile strength loss, having thereon from 5% to 15% based on the dry weight of the material of a wet cured water-soluble dimethylol melamine and from 1% to about 15 based on the dry weight of the material of a dry cured water-soluble dimethylol ethylene urea.

References Cited by the Examiner UNITED STATES PATENTS 2,763,574 9/1956 Ruperti l17-138.5 2,898,238 8/1959 Van Loo et a1. 1l7-139.4 2,917,412 12/ 1959 Reinhardt et al 117l39.4 3,050,419 8/1962 Ruperti Ill-138.5 3,138,802 6/ 1964 Getchell 2- 243 3,197,270 7/ 1965 Roth 117l38.5 X

WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner.

Dedication 3,311,496. William Julius Van Loo, Jr., Middlesex, NJ. PROCESS FOR PRO- DUCING ROT AND WRINKLE RESISTANT CELLULOSE CONTAINING TEXTILE AND TEXTILE OBTAINED THERE- WI'I'H. Patent dated Mar. 28, 1967. Dedication filed Mar. 4, 1983, by the assignee, American Cyanamid Co.

Hereby dedicates the remaining term of said patent to the Public.

[Oflicial Gazette May 3], 1983.] 

1. A PROCESS FOR IMPARTING TO CELLULOSE-CONTAINING TEXTILE MATERIALS IMPROVED WRINKLE RECOVERY WITH LOW TENSILE STRENGTH LOSSES, WHICH COMPRISES TREATING THE MATERIAL WITH AN AQUEOUS IMPREGNATING SOLUTION OF AN AMINOPLAST CONTAINING A CURING CATALYST SO AS TO APPLY FROM 1% TO ABOUT 30% BASED ON THE WEIGHT OF THE MATERIAL OF SAID AMINOPLAST, CURING SAID AMINOPLAST IMPREGNATED MATERIAL IN THE PRESENCE OF WATER WITHOUT SUBSTANTIALLY DRYING THE MATERIAL, SUBSEQUENTLY APPLYING TO SAID TREATED MATERIAL AN AQUEOUS SOLUTION OF A WATER-SOLUBLE CREASEPROOFING HARDENABLE AMINOPLAST CONTAINING A CURING CATALYST SO AS TO APPLY FROM 1% TO ABOUT 15% BASED ON THE DRY WEIGHT OF THE MATERIAL OF SAID AMINOPLAST AND HEAT CURING THE THUS TREATED MATERIAL. 